CN111423705B - Environment-friendly asphalt modifier and preparation method and application thereof - Google Patents
Environment-friendly asphalt modifier and preparation method and application thereof Download PDFInfo
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- CN111423705B CN111423705B CN202010275964.2A CN202010275964A CN111423705B CN 111423705 B CN111423705 B CN 111423705B CN 202010275964 A CN202010275964 A CN 202010275964A CN 111423705 B CN111423705 B CN 111423705B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses an environment-friendly asphalt modifier and a preparation method and application thereof, wherein the asphalt modifier comprises the following components in parts by mass: 25-85 parts of medium-high carbon hydroxy fatty acid and a polymer thereof; 10-70 parts of sulfonated fatty acid polyglycerol ester; 5-10 parts of polysiloxane and derivatives thereof; the preparation method comprises the following steps: weighing the raw materials according to the formula ratio, and then mixing and stirring at 40-50 ℃ to prepare the traditional Chinese medicine composition; and an asphalt mixture containing the environment-friendly asphalt improver; the asphalt modifier disclosed by the invention is low in preparation cost, can simultaneously improve the thermal stability and the tensile resistance of asphalt, plays a toughening effect, enhances the anti-rutting capability at high temperature and the anti-cracking capability at low temperature, improves the wear resistance, prolongs the service life and the like.
Description
Technical Field
The invention belongs to the technical field of asphalt modification, and particularly relates to an environment-friendly asphalt modifier as well as a preparation method and application thereof.
Background
Bitumen is a residue obtained after evaporation of most volatile oils in crude oil components, wherein bitumen has physical properties that remain in a liquid or semi-solid state with high viscosity at high temperatures, but hardens at room temperature or lower. In addition, since asphalt has such properties: asphalt is widely used for building materials, such as road paving materials or waterproof materials, because of its good moldability, high water resistance, electrical insulation and adhesiveness, and excellent chemical stability. However, asphalt has a limitation in that plastic deformation occurs during use when asphalt is exposed to high temperature for a long time and cracks occur at low temperature due to external impact.
There are many changes occurring to modern highways and roads at the same time: the traffic flow and the driving frequency are increased rapidly, the axle weight of a freight car is increased continuously, lane-divided one-way driving is generally carried out, and the anti-flow property of the road surface, namely the anti-rutting capability at high temperature is required to be further improved; the flexibility and elasticity, namely the capability of resisting cracking at low temperature are improved; improving the abrasion resistance and prolonging the service life. These changes in the use environment present a significant challenge to the performance of petroleum asphalt.
In the prior art, the asphalt is modified to improve the corresponding performance of the asphalt, but the modification cost is too high (the modified material is usually 2 to 7 times higher than the common petroleum asphalt) and the practical application of the modified material is greatly limited.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide an improved asphalt modifier which is low in preparation cost, can simultaneously improve the thermal stability and tensile resistance of asphalt, has a toughening effect, enhances the anti-rutting capability at high temperature and the anti-cracking capability at low temperature, improves the wear resistance, prolongs the service life and the like.
The invention also provides a preparation method of the asphalt modifier.
The invention also provides an asphalt composition containing the asphalt modifier.
In order to achieve the purpose, the invention adopts the technical scheme that: the environment-friendly asphalt modifier comprises the following components in parts by weight:
25-85 parts of medium-high carbon hydroxy fatty acid and a polymer thereof;
10-70 parts of sulfonated fatty acid polyglycerol ester;
5-10 parts of polysiloxane and derivatives thereof.
According to some preferred and specific aspects of the present invention, the asphalt modifier is composed of the following components in parts by mass:
30-80 parts of medium-high carbon hydroxy fatty acid and a polymer thereof;
15-60 parts of sulfonated fatty acid polyglycerol ester;
5-10 parts of polysiloxane and derivatives thereof.
According to the invention, the medium-high carbon hydroxy fatty acid and the polymer thereof are by-products at the bottom of the tower in the distillation and refining process of preparing fatty acid from castor oil saponin. Specifically, the bottom by-product can be obtained commercially or obtained in a distillation refining process for fatty acid production by conventional castor oil saponin in the art.
In some embodiments of the present invention, the conventional castor oil saponin-derived fatty acid distillation refining process comprises the steps of:
1) acidifying: placing castor oil saponin in an acidification kettle, adding concentrated sulfuric acid according to the mass ratio of 0.2-0.5% of the saponin, and acidifying for 1-1.5h to obtain a mixture of fatty acid and neutral oil;
2) hydrolysis: transferring the mixture obtained in the step 1) into a hydrolysis kettle, adding 10% sulfuric acid aqueous solution according to the mass ratio of 1/3-1/3.5 of saponin, and hydrolyzing for 2-3h to obtain crude fatty acid;
3) and (3) distillation: carrying out vacuum distillation on the crude fatty acid obtained in the step 2), wherein the vacuum degree P is more than or equal to 0.1Mpa, the temperature T is 250-;
4) and (3) finished product: the by-products at the bottom of the tower are medium-high carbon hydroxy fatty acid and polymers thereof.
According to some specific aspects of the present invention, the polysiloxane and its derivatives are one or more selected from the group consisting of polysiloxane, polysilica resin, polyborosiloxane, all of which are commercially available.
According to some preferred aspects of the invention, the polysiloxane has a number average molecular weight of 50000-100000, the R/Si (number of organic groups) value of the silicone resin is from 0.8 to 1.2, and the Si/B (ratio of silicon to boron) value of the polyborosiloxane is from 3.3 to 3.8.
According to some preferred aspects of the present invention, the viscosity of the sulfonated fatty acid polyglyceride is 2500-3000mPa s.
According to some preferred aspects of the present invention, the sulfonated fatty acid polyglyceryl esters have the following structure:
wherein R is C4-22Alkyl, R' is C1-3An alkyl group. According to some preferred and specific aspects of the present invention, R may be a linear or branched alkyl group having a carbon number of 4 to 22, and R' is methyl, ethyl or propyl.
According to some preferred aspects of the present invention, the sulfonated fatty acid polyglyceryl ester is prepared by the following method: (1) controlling the temperature of the fatty acid polyglycerol ester to 35-40 ℃, and controlling the temperature of liquid sulfur trioxide to 50-55 ℃ for later use; (2) according to the mol ratio of 1: 1.2-1.5, weighing medium fatty acid polyglycerol ester and liquid sulfur trioxide in a reaction vessel for sulfonation reaction; (3) heating and aging the sulfonation product obtained in the step (2) until the viscosity of the product is 2500-3000mPa & s.
According to some preferred and specific aspects of the present invention, in the step (2), the sulfonation reaction is controlled to be performed at 55 to 70 ℃.
According to some preferred and specific aspects of the present invention, in the step (3), the temperature of the heat aging is controlled to be 70 to 80 ℃.
According to some specific aspects of the present invention, in the step (2), the sulfonation reaction is carried out for 0.9 to 1.2 hours.
According to some specific aspects of the present invention, in the step (3), the heat aging time is 0.5 to 1 hour.
According to the invention, the fatty acid polyglycerol ester is a tower bottom byproduct in an animal and vegetable oil esterification modification distillation refining process, and the animal and vegetable oil is one or a combination of more of beef and mutton fat, lard oil, duck oil, fox oil, coconut oil, olive oil, castor oil, soybean oil, corn oil, palm oil, rapeseed oil, cottonseed oil, peanut oil and sunflower seed oil. Specifically, the tower bottom by-product can be obtained commercially or prepared by the conventional esterification, modification and distillation refining procedures of animal and vegetable fats and oils in the field.
In some embodiments of the present invention, the conventional animal and vegetable fat esterification modification distillation refining process comprises the following steps:
1) esterification: according to the mass ratio of 1: 0.2-0.25: respectively weighing animal and vegetable oil, methanol and methanesulfonic acid 0.002-0.005, placing in a reaction kettle, reacting at the temperature T of 130-;
2) ester exchange: weighing 0.2-0.6% of KOH according to the mass of the animal and vegetable oil, dissolving the KOH in 25-35% of methanol, adding the esterification reaction liquid, controlling the temperature to be 55-65 ℃, and stirring for reaction for 1 hour;
3) removing glycerin: performing transesterification on the reaction solution, separating liquid, taking an upper methyl ester phase, and removing lower glycerol;
4) methanol removal: removing alcohol from the upper methyl ester phase, controlling the temperature to be 100 ℃ and 120 ℃ to evaporate the methanol, and standing for 20min to divide the glycerol after removing the alcohol;
6) and (3) reduced pressure distillation: distilling the dealcoholized crude methyl ester phase, wherein the vacuum degree P is more than or equal to 0.1MPa, the temperature T is 225-275 ℃, and the distillate at the top of the tower is refined methyl ester;
7) and (3) finished product: the by-product at the bottom of the tower is the fatty acid polyglycerol ester.
The invention provides another technical scheme that: the preparation method of the environment-friendly asphalt modifier comprises the following steps: weighing the raw materials according to the formula ratio, and then mixing and stirring at 40-50 ℃ to prepare the traditional Chinese medicine.
The invention provides another technical scheme that: an asphalt mixture, which comprises asphalt and the environment-friendly asphalt modifier; the addition amount of the environment-friendly asphalt modifier is 1-30% of the feeding amount of the asphalt, preferably 5-25%, and more preferably 5-20% by mass percentage.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the asphalt modifier is prepared by compounding three specific polymers, so that the thermal stability and the tensile resistance of asphalt can be improved, the toughening effect is achieved, the anti-rutting capability at high temperature and the anti-cracking capability at low temperature are enhanced, the wear resistance is improved, and the service life is prolonged; but also can reduce the viscosity of the asphalt and increase the dispersion uniformity of the asphalt, thereby effectively reducing the construction temperature, being safe and efficient and saving energy consumption; in addition, the asphalt modifier can prevent combustion decomposition products possibly existing in the construction process from escaping to a certain extent, inhibit the thermal decomposition of high polymer materials, achieve the purposes of flame retardance, low smoke, low toxicity and the like, further reduce the smoke emission in the construction process, and avoid polluting the environment and damaging the human health.
Meanwhile, the asphalt modifier disclosed by the invention adopts natural biological source raw materials, and wastes are comprehensively utilized, so that the resource waste is avoided, and the cost is well reduced.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples; it is to be understood that these embodiments are provided to illustrate the general principles, essential features and advantages of the present invention, and the present invention is not limited in scope by the following embodiments; the implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments.
Not specifically illustrated in the following examples, all starting materials are commercially available or prepared by methods conventional in the art.
The medium-high carbon hydroxy fatty acid and the polymer thereof are both the by-products at the bottom of the distillation refining process for preparing fatty acid from castor oil saponin in the field; the polyglycerol fatty acid ester is a tower bottom byproduct from the esterification modification distillation refining process of animal and vegetable oil and fat which is conventional in the field, wherein the animal and vegetable oil and fat is one or a combination of more of beef and mutton fat, lard oil, duck oil, fox oil, coconut oil, olive oil, castor oil, soybean oil, corn oil, palm oil, rapeseed oil, cottonseed oil, peanut oil and sunflower seed oil.
The sulfonated fatty acid polyglycerol ester (specifically, sulfonated coconut oleic acid polyglycerol ester, sulfonated beef tallow polyglycerol ester, sulfonated coconut oleic acid polyglycerol ester, sulfonated cottonseed oleic acid polyglycerol ester, sulfonated chicken and duck oil polyglycerol ester, sulfonated rapeseed oleic acid polyglycerol ester, sulfonated soybean oleic acid polyglycerol ester, sulfonated peanut oleic acid polyglycerol ester, sulfonated sunflower seed oleic acid polyglycerol ester, sulfonated lard oil polyglycerol ester or sulfonated mutton fat polyglycerol ester) in the following examples is prepared by the following preparation method:
(1) preheating: controlling the temperature of the fatty acid polyglycerol ester to 37 +/-1 ℃, and controlling the temperature of liquid sulfur trioxide to 53 +/-1 ℃ for later use;
(2) sulfonation: according to the mol ratio of 1: 1.3 weighing medium fatty acid polyglycerol ester and liquid sulfur trioxide, and carrying out sulfonation reaction in a three-neck flask to prepare a sulfonated product, wherein the stirring speed is 400rpm, the reaction temperature is 65 ℃, and the reaction time is 1 h;
(3) aging: and further heating and aging the prepared sulfonated product, and stopping the reaction when the viscosity of the product reaches 2800 +/-100 mPa & s to obtain the sulfonated fatty acid polyglycerol ester product, wherein the aging temperature is 75 ℃ and the aging time is 1 h.
Hereinafter, the polysiloxane used has a number average molecular weight of about 70000-80000, the R/Si (number of organic groups) value of the polysiloxane resin used is about 1.0, and the Si/B (ratio of silicon to boron) value of the polyborosiloxane used is about 3.5.
Example 1
The embodiment provides an asphalt modifier and a preparation method thereof: according to the parts by weight: 30 parts of medium-high-carbon hydroxyl fatty acid and polymer thereof, 40 parts of sulfonated coconut oleic acid polyglycerol ester, 20 parts of sulfonated tallow polyglycerol ester and 10 parts of polysiloxane, and mixing and stirring the components at the stirring temperature of 45 ℃, the stirring speed of 100rpm and the stirring time of 15min to obtain the asphalt modifier.
Example 2
The embodiment provides an asphalt modifier and a preparation method thereof: according to the parts by weight: 50 parts of medium-high carbon hydroxy fatty acid and polymer thereof, 20 parts of sulfonated palmitoleic acid polyglycerol ester, 20 parts of sulfonated cottonseed oleic acid polyglycerol ester and 10 parts of silicone resin, and mixing and stirring the components at the stirring temperature of 43 ℃, the stirring speed of 110rpm and the stirring time of 20min to obtain the asphalt modifier.
Example 3
The embodiment provides an asphalt modifier and a preparation method thereof: according to the parts by weight: 45 parts of medium-high carbon hydroxyl fatty acid and polymer thereof, 40 parts of sulfonated stearic acid polyglycerol ester, 10 parts of sulfonated chicken duck oil polyglycerol ester and 5 parts of polyborosiloxane, and mixing and stirring the components at the stirring temperature of 46 ℃, the stirring speed of 120rpm and the stirring time of 13min to obtain the asphalt modifier.
Example 4
The embodiment provides an asphalt modifier and a preparation method thereof: according to the parts by weight: 35 parts of medium-high carbon hydroxy fatty acid and polymer thereof, 50 parts of sulfonated rapeseed oleic acid polyglycerol ester, 8 parts of sulfonated soybean oleic acid polyglycerol ester and 7 parts of polysiloxane, and mixing and stirring the components at the stirring temperature of 48 ℃, the stirring speed of 130rpm and the stirring time of 12min to obtain the asphalt modifier.
Example 5
The embodiment provides an asphalt modifier and a preparation method thereof: according to the parts by weight: 60 parts of medium-high carbon hydroxy fatty acid and polymer thereof, 30 parts of sulfonated peanut oleic acid polyglycerol ester, 5 parts of silicone resin and 5 parts of polysiloxane, and mixing and stirring the components at the stirring temperature of 50 ℃, the stirring speed of 100rpm and the stirring time of 18min to obtain the asphalt modifier.
Example 6
The embodiment provides an asphalt modifier and a preparation method thereof: according to the parts by weight: 70 parts of medium-high carbon hydroxy fatty acid and polymer thereof, 10 parts of sulfonated sunflower seed oleic acid polymerized glyceride, 10 parts of sulfonated lard polymerized glyceride, 5 parts of silicone resin and 5 parts of polyborosiloxane, and mixing and stirring the components at the stirring temperature of 47 ℃, the stirring speed of 150rpm and the stirring time of 20min to obtain the asphalt modifier.
Example 7
The embodiment provides an asphalt modifier and a preparation method thereof: according to the parts by weight: 80 parts of medium-high carbon hydroxy fatty acid and polymer thereof, 15 parts of sulfonated cottonseed oleic acid polyglycerol ester and 5 parts of silicone resin, and mixing and stirring the components at the stirring temperature of 50 ℃, the stirring speed of 150rpm and the stirring time of 15min to obtain the asphalt modifier.
Example 8
The embodiment provides an asphalt modifier and a preparation method thereof: according to the parts by weight: 55 parts of medium-high carbon hydroxyl fatty acid and polymer thereof, 20 parts of sulfonated soybean oleic acid polyglycerol ester, 15 parts of sulfonated mutton fat polyglycerol ester, 5 parts of silicone resin and 5 parts of polyborosiloxane, and the asphalt modifier is obtained by mixing and stirring at the stirring temperature of 42 ℃, the stirring speed of 120rpm and the stirring time of 16 min.
Performance testing
The asphalt modifier prepared in examples 1 to 8 of the present invention was subjected to a performance effect test: indexes of softening point, ductility and penetration are respectively detected in SH/T0522-2010 road petroleum asphalt according to a GB/T4507 asphalt softening point determination method (a ring and ball method), a GB/T4508 asphalt ductility determination method and a GB/T4509 asphalt penetration determination method:
1. the detection result of adding the asphalt modifier (the addition amount is 5 percent of the No. 200 petroleum asphalt) into No. 200 petroleum asphalt is as follows:
2. the detection result of adding the asphalt modifier (the addition amount is 10 percent of the No. 100 petroleum asphalt) into No. 100 petroleum asphalt is as follows:
as can be seen from the test data in the table above, the asphalt modifier prepared by the invention has the advantages of increased softening point (thermal stability), ductility (anti-stretching effect) and penetration, and obvious effects of toughening, lubrication, viscosity reduction and dispersion.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (9)
1. The environment-friendly asphalt modifier is characterized by comprising the following components in parts by mass:
25-85 parts of medium-high carbon hydroxy fatty acid and a polymer thereof;
10-70 parts of sulfonated fatty acid polyglycerol ester;
5-10 parts of polysiloxane and derivatives thereof.
2. The environment-friendly asphalt improver according to claim 1, wherein the asphalt improver comprises the following components in parts by mass:
30-80 parts of medium-high carbon hydroxy fatty acid and a polymer thereof;
15-60 parts of sulfonated fatty acid polyglycerol ester;
5-10 parts of polysiloxane and derivatives thereof.
3. The environment-friendly asphalt improver according to claim 1 or 2, wherein the medium-high hydroxyl fatty acid and the polymer thereof are by-products at the bottom of a distillation refining process for preparing fatty acid from castor oil saponin; and/or the polysiloxane and the derivatives thereof are one or more selected from polysiloxane, polysilicone resin and polyborosiloxane.
4. The environment-friendly asphalt improver as recited in claim 1 or 2, wherein the viscosity of the sulfonated fatty acid polyglycerin ester is 2500-3000 mPa-s.
5. The environment-friendly asphalt improver according to claim 1 or 2, wherein the sulfonated fatty acid polyglycerol ester is prepared by the following method: (1) controlling the temperature of the fatty acid polyglycerol ester to 35-40 ℃, and controlling the temperature of liquid sulfur trioxide to 50-55 ℃ for later use; (2) according to the mol ratio of 1: 1.2-1.5, weighing fatty acid polyglycerol ester and liquid sulfur trioxide in a reaction vessel for sulfonation reaction; (3) heating and aging the sulfonation product obtained in the step (2) until the viscosity of the product is 2500-3000mPa & s.
6. The environment-friendly asphalt improver according to claim 5, wherein in the step (2), the sulfonation is controlled to be carried out at 55 to 70 ℃; and/or, in the step (3), the temperature of the heating aging is controlled to be 70-80 ℃.
7. The environment-friendly asphalt improver according to claim 5, wherein the polyglycerol fatty acid ester is a byproduct at the bottom of a distillation refining process for esterification modification of animal and vegetable oils and fats, and the animal and vegetable oils and fats are one or a combination of more selected from the group consisting of tallow, lard, duck oil, fox oil, coconut oil, olive oil, castor oil, soybean oil, corn oil, palm oil, rapeseed oil, cottonseed oil, peanut oil and sunflower seed oil.
8. A method for preparing the environment-friendly asphalt improver as described in any one of claims 1 to 7, wherein the method comprises the following steps: weighing the raw materials according to the formula ratio, and then mixing and stirring at 40-50 ℃ to prepare the traditional Chinese medicine.
9. An asphalt mixture comprising asphalt, wherein the asphalt mixture further comprises the environment-friendly asphalt improver as defined in any one of claims 1 to 7; the addition amount of the environment-friendly asphalt modifier is 1-30% of the feeding amount of the asphalt by mass percentage.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB252258A (en) * | 1925-02-23 | 1926-05-25 | Horatio Whitehead Hutton | Improvements in emulsions of bituminous material |
| GB662237A (en) * | 1948-04-06 | 1951-12-05 | Bataafsche Petroleum | Improvements in or relating to bituminous compositions |
| US4861377A (en) * | 1988-04-18 | 1989-08-29 | Westvaco Corporation | Cationic aqueous bituminous emulsion-aggregate slurries |
| KR101282174B1 (en) * | 2012-12-11 | 2013-07-04 | 금호석유화학 주식회사 | Warm-mix recycled asphalt additives comprising fat residue and warm-mix recycled asphalt mixture comprising the same |
| CN104559237B (en) * | 2013-10-22 | 2017-01-25 | 中国石油化工股份有限公司 | Non-ionic liquid crystal asphalt warm mixing agent and preparation method thereof |
| CA2965697C (en) * | 2014-11-03 | 2020-08-18 | Flint Hills Resources, Lp | Asphalt binders containing a glyceride and fatty acid mixture and methods for making and using same |
| US20160376440A1 (en) * | 2015-06-26 | 2016-12-29 | Green Paving Solutions, Llc | Asphalt additive, asphalt compositions and products comprising such additive, asphalt surfaces comprising such additive, methods of making and using such additive, compositions, surfaces and products |
| CN104987735B (en) * | 2015-07-06 | 2017-12-15 | 交通运输部公路科学研究所 | A kind of silicon-modified epoxy pitch and compound |
| US10323148B1 (en) * | 2016-05-26 | 2019-06-18 | Marathon Petroleum Company Lp | Method of making an asphalt composition containing ester bottoms |
| CN108456431A (en) * | 2018-03-14 | 2018-08-28 | 洛阳璟信公路工程科技发展有限公司 | A kind of highway asphalt environmental protection cold-repairing material and its production technology |
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